DE3743486A1 - SOFT, THERMOPLASTICALLY PROCESSABLE, POLYAMIDE CONTAINING POLYMER ALLOYS - Google Patents

Description

The invention relates to soft, rubbery, thermoplastic processable polymer alloys on the basis from 10 to 50% by weight (cyclo) aliphatic, thermoplastic Polyamides and 90 to 50% by weight of special, crosslinked, particulate alkyl acrylate copolymer rubbers, which are used to manufacture rubbery, elastic Molding compounds are suitable.

The invention also relates to a method for its Manufacturing.

Flexible polymer blends based on certain Graft polymers and acrylate copolymer rubbers are known and have become thermoplastic in the field processable elastomer proven.

In contrast, polyamides, such as polyamide-6 or polyamide-66, on the other hand represent technically significant thermoplastics which are characterized by hardness, rigidity,  good practical heat resistance and high Characterize stability against the influence of solvents.

It has now surprisingly been found that one can the combination of preferably smaller proportions of such Polyamides and preferably predominant proportions certain, special, cross-linked, particulate Acrylate rubber copolymer despite the presence of the hard, non-elastic polyamide and despite the one highly cross-linked acrylate copolymer rubbers homogeneous, soft, flexible polymer alloys (polymer mixtures) can reach. These polymer alloys have excellent thermoplastic processability, good solvent resistance, high aging stability and especially good adhesion other plastic materials, especially on polyamides and polyurethanes.

The invention thus relates to soft, thermoplastic processable polymer alloys with elastic Properties, characterized by a salary of

• a) 10 to 50 wt .-%, preferably 10 to 35 wt .-% of one thermoplastic, amorphous or semi-crystalline, preferably semi-crystalline, aliphatic and / or cycloaliphatic polyamide,
• b) 90 to 50% by weight, preferably 90 to 65% by weight, of a partially crosslinked, particulate rubber copolymer
  • b1) at least 60% by weight, preferably at least 65% by weight, in particular 95 to 60% by weight, based on b), of a C₂-C₈ alkyl acrylate with primary or secondary alkyl groups, and
  • b2) 4.45 to 40 wt .-%, preferably 10 to 35 wt .-%, in particular 4.45 to 33 wt .-%, based on b), of at least one monomer from the series acrylonitrile or C₁-C₆-alkyl methacrylates with primary and / or secondary alkyl groups,
  • b3) 0 to 10% by weight, preferably 0 to 6% by weight, in particular 0.5 to 5% by weight, of at least one monomer from the series of a tertiary alkyl (meth) acrylate, (meth) acrylic acid or maleic anhydride , such as
  • b4) 0 to 5% by weight, preferably 0 to 2% by weight, in particular 0.05 to 2% by weight, of a crosslinking monomer with at least two olefinically unsaturated groups,
• wherein the rubber polymer b) has a gel content from 20 to 99% by weight, preferably 50 to 99% by weight, in particular from 70 to 99% by weight, and one average particle diameter (d₅₀) from 0.09 to 1.2 µm, preferably 0.09 to 0.8 µm and in particular from 0.1 to 0.4 µm.

The polymer alloys can also be customary Additives contained in usual amounts.  

Suitable polyamides a) for the purposes of the invention amorphous and in particular semi-crystalline, aliphatic and / or cycloaliphatic polyamides or their mixtures. So as partially crystalline polyamides for the invention Polymer alloys polyamide 6, polyamide 6,6 and copolymers of these two components are used will. Also come, for example, partially crystalline Consider polyamides, their acid components all or part of straight-chain or branched, aliphatic or cycloaliphatic dicarboxylic acids, e.g. B. from adipic acid, suberic acid, sebacic acid and / or Azelaic acid and / or cyclohexanedicarboxylic acids, and whose diamine component consists of straight-chain or branched, aliphatic or cycloaliphatic diamines, for example from hexamethylenediamine and / or 2,2,4- Trimethylhexamethylene diamine and / or 2,4,4-trimethylhexamethylene diamine and / or isophoronediamine. The Manufacturing methods and compositions of such polyamides are known from the prior art. Furthermore are to be mentioned polyamides that are made up entirely or partially Lactams with 4 to 12 carbon atoms, optionally under Use of one or more of the above-mentioned diamine or dicarboxylic acid starting components will.

According to the prior art, the amorphous polyamides can be known products are used. You will get by polycondensation of aliphatic and / or cycloaliphatic diamines such as 2- or 3-methylhexane diamine-1,6, propylene diamine, hexamethylene diamine, decamethylene diamine, 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine,  Bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine and its isomers (isophoronediamine), 2.5- and / or 2,6-bis (aminomethyl) norbornane and / or 1,4- Dimethylcyclohexane, with aliphatic and / or cycloaliphatic Dicarboxylic acids such as oxalic acid, adipic acid, Methyl adipic acid, azelaic acid, decanedicarboxylic acid, Heptadecanedicarboxylic acid, so-called dimer acids, 2,2,4- and / or 2,4,4-trimethyladipic acid.

Of course, copolymers which are obtained by polycondensation of several monomers can also be used, furthermore those copolymers which are prepared with the addition of aminocarboxylic acids such as ε- aminocaproic acid, ω -aminoundecanoic acid or ω- aminolauric acid or their lactams.

Particularly preferred polyamides based on lactams or Aminocarboxylic acids are polyamide-6, polyamide-66, polyamide-11 and polyamide 12, in particular polyamide 12 and the polyamide-6.

For the purposes of the invention, polymers b) are partially crosslinked, particulate rubber copolymers

• b1) the stated amounts of a primary or secondary C₂-C₈ alkyl acrylates, such as ethyl, propyl, n-butyl, iso-butyl or n-hexyl acrylate,  
• b2) the stated amounts of at least one monomer the series of acrylonitrile and C₁-C₆ alkyl methacrylate, especially methyl methacrylate, but preferred Acrylonitrile, and
• b3) the stated amounts of a tertiary alkyl (meth) - acrylate, especially tert-butyl acrylate, (meth) - Acrylic acid or maleic anhydride,
• b4) if necessary, the stated amounts of a double or higher functional unsaturated compound as crosslinking monomers.

Crosslinking monomers b4) are alkyl methacrylate, Ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic Compounds containing at least 3 copolymerizable have ethylenically unsaturated double bonds, prefers. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, Triallyl isocyanurate, trivinyl cyanurate, trisacryloyl hexyhydro-s-triazine and the triallylbenzenes.

The amount of crosslinking monomers is in particular 0.05 to 2 wt .-%, based on the rubber copolymer b). With cyclic, crosslinking monomers with at least 3 ethylenically unsaturated double bonds it is advantageous not to exceed 1% by weight based on Rubber copolymer to use.

The rubber copolymers d) have gel contents of 20 to 99 wt .-% and small average particle diameter  (d₅₀) preferably from 0.09 to 0.8 µm.

Component b) can be prepared in a known manner take place, e.g. B. by radical, aqueous emulsion polymerization in the presence of anionic, surface-active Fabrics, especially in the temperature range from 40 to 95 ° C, preferably at 55 to 80 ° C. In the case, that no crosslinking monomers b4) are used, can the rubber copolymers subsequently are networked in a known manner, for. B. by peroxide treatment or through radiation cross-linking.

Contain preferred polymer alloys according to the invention as component a) polyamide-6, polyamide-12, polyamide- 11 or polyamide-66, but especially polyamide-12 and as a rubber-like copolymer component Alkyl acrylate (b1) and acrylonitrile (b2) by polymerization with crosslinking by means of copolymerization with a portion (b4) of trifunctional allyl compounds, especially triallyl cyanurate. Such Polymer alloys have high crosslinking (with gel contents greater than 70% by weight, in particular greater than 85% by weight).

The polymer alloys can optionally be conventional Additives as they are basically from the prior art are known, e.g. B. lubricants, pigments, antioxidants or any stabilizers, fillers or reinforcing fibers, or also polyamide plasticizers, contain. Examples are plasticizers from the series Sulfonamides, bisphenols or halogenated aromatics.  

The preparation of the mixtures (alloys) can be based on usual ways are done by making up their emulsion by conventional coagulation processes and, for example Direct drying process (spray drying) isolated and optionally purified polymer components b) using known compounding units such as kneaders, Screws or rollers at elevated temperatures with the Polyamide components a) and optionally other additional components and additives of the above as additives mentioned type are mixed.

The invention also relates to a method for Production of soft, thermoplastically processable Polymer alloys with elastic properties Mixing two components using known compounding units at elevated temperatures in the Melt, characterized in that one

• a) 10 to 50 wt .-%, preferably 10 to 35 wt .-%, a thermoplastic, amorphous or partially crystalline aliphatic polyamide, preferably a partially crystalline aromatic polyamide, in particular polyamide-6, polyamide-66, polyamide-11 and / or polyamide -12
  With
• b) 90 to 50% by weight, preferably 90 to 65% by weight, of a partially crosslinked, particulate rubber polymer
  • b1) at least 60% by weight, preferably at least 65% by weight, in particular 95 to 60% by weight, based on b), of a C₂-C₈-alkyl acrylate with primary or secondary alkyl groups,
  • b2) 4.45 to 40% by weight, preferably 10 to 35% by weight, in particular 4.45 to 33% by weight, based on b), of at least one monomer from the series of acrylonitrile or C₁-Cmeth-alkyl methacrylates with primary and / or secondary alkyl groups,
  • b3) 0 to 10% by weight, preferably 0 to 6% by weight, in particular 0.5 to 5% by weight, of at least one monomer from the series of a tertiary alkyl (meth) acrylate, (meth) acrylic acid or maleic anhydride , such as
  • b4) 0 to 5% by weight, preferably 0 to 2% by weight, in particular 0.05 to 2% by weight, of a crosslinking monomer with at least two olefinically unsaturated groups,
• wherein the rubber polymer b) has a gel content from 20 to 99% by weight, preferably 50 to 99% by weight, in particular from 70 to 99% by weight, and one average particle diameter (d₅₀) from 0.09 to 1.2 µm, preferably 0.09 to 0.8 µm and in particular from 0.1 to 0.4 µm.

mixed.  

Molding compositions from these polymer alloys according to the invention have many properties both more common Rubber polymers or thermoplastic Elastomers together; its special is to be emphasized Property combination of stretching behavior, softness and strength. In particular, they show a combination high tensile strength, preferably <5 MPa, in particular 10 MPa, a high, largely reversible elongation, is preferred of <80%, especially 100%, a considerable one Tear resistance, preferably of <25 MPa, in particular 37 MPa and a remarkable Shore hardness A / D, preferred of <70/15, especially 80/25. Depending on the proportion from a) and b) these mechanical Properties vary, and in a particularly beneficial way the cold resistance (e.g. compared to Modify and improve plasticized PVC films).

Since component b) is a highly crosslinked copolymer, have those made from the polymer alloy Molding compounds extremely low levels of volatile or migrating contaminants in comparison to known molding compounds with rubber-elastic properties, e.g. B. plasticized PVC or polyamide. To be highlighted are still the special insensitivity compared to technically relevant solvent systems and their high resistance to aging. The polymer alloys are suitable for the production of coatings, sealants, Foils, damping materials and rubber articles.  

Examples 1) Polyamides used a)

• 1.1) Polyamide-12 with a relative solution viscosity (in m-cresol at 0.5 g / 100 ml at 25 ° C) of 2.1 (Vestamid® L 2122 P - Hüls AG, Marl)
• 1.2) Polyamide-12 with a relative solution viscosity (in m-cresol at 0.5 g / 100 ml at 25 ° C) from 1.63 (Vestamid® WS)
• 1.3) Polyamide-6 with a relative solution viscosity of 3.1 (as a 1% solution in m-cresol at 25 ° C) (Durethan® B 31 F - BAYER AG, D-5090 Leverkusen)

2) Components used b) 2.1) Rubber copolymer in the sense of the invention

A solution of 2.5% by weight is Share Na salt of C₁₄-C₁₈ alkyl sulfonic acids in 750 parts by weight of water presented. After heating up 70 parts by weight of the monomer solution are added to 70.degree A) and initiates the polymerization through Add a solution of 3.5 parts by weight of potassium peroxide sulfate in 50 parts by weight of water. Dosed at 70 ° C the rest of solution A) and the solution B) evenly within 6 hours in the reactor and polymerizes within 4 hours  out. It becomes a latex with a polymer solids content of 37% by weight, an average particle diameter (d₅₀) of 0.18 µm and a gel content (in DMF) of 98% by weight.

Solution A:
1105 parts by weight of n-butyl acrylate (b1)
7 parts by weight of triallyl cyanurate (b4)
474 parts by weight of acrylonitrile (b2)
Solution B:
30 parts by weight of Na salt of C₁₄-C₁₈ alkyl sulfonic acid
1790 parts by weight of water

2.2) Rubber copolymer in the sense of the invention

A rubber copolymer made from n-butyl acrylate, Acrylonitrile, triallyl cyanurate and tert-butyl acrylate manufactured by: according to regulation 2.1) polymerized as solution A:

Solution A:
1030 parts by weight of n-butyl acrylate (b1)
7 parts by weight of triallyl cyanurate (b4)
474 parts by weight of acrylonitrile (b2)
75 parts by weight of tert-butyl acrylate (b3)
(Solution B: as in 2.1)

It becomes a latex with a polymer solid from 37 wt .-%, an average particle diameter (d₅₀) of 0.16 µm and a gel content (in DMF) of Received 97 wt .-%.  

2.3) Rubber polymer for comparison

A solution of 5 parts by weight is placed in a reactor Na salt of C₁₄-C₁₈ alkyl sulfonic acids in 1030 wt. Parts of water submitted. After heating to 70 ° C 80 parts by weight of monomer solution A) are added and initiates the polymerization by adding a solution of 4 parts by weight of potassium peroxydisulfate in 100 parts by weight of water. At 70 ° C you meter the Rest of solution A) and solution B) evenly into the reactor within 5 hours and polymerizes within 4 hours. It will a latex with a polymer solids content of 30 wt .-%, an average particle diameter (d₅₀) of 0.20 µm and a gel content (in DMF) of 95% by weight.

Solution A:
995 parts by weight of n-butyl acrylate (b1)
5 parts by weight of triallyl cyanurate (b4)
Solution B:
25 parts by weight of Na salt of C₁₄-C₁₈ alkyl sulfonic acid
700 parts by weight of water

For the measurement of the mean particle diameter d ₍₅₀₎ see W. Scholtan u. H. Lange, Kolloid-Zeitschrift and Z. für Polymer, 250 (1972), pp. 787-796.

To measure the gel content in DMF were used 0.5% solutions in tetrahydrofuran at 25 ° C Gel fraction separated using an ultracentrifuge and balanced after drying (see M. Hoffmann et al, Polymer analysis, Georg Thieme-Verlag, Stuttgart, 1977, p. 172, 289 - part A and p. 341 part B.).  

3) Production and properties of the polymer alloys

The latices 2) are stabilized with 1% by weight (based on polymer content) phenolic antioxidants coagulated with aqueous magnesium sulfate solution, washed and dried at 70 ° C.

Components a) and b) become polymer alloys 3.1 to 3.5 (see table 1) on a roller at 230 ° C Compounded for 5 minutes; doing so as a processing aid 2.8% by weight of ester wax (Hoechstwachs®-C, Hoechst AG, Frankfurt-Hoechst, Federal Republic Germany). Then the formed rolled skin pressed to test specimens at 240 ° C. In Table 2 is the property comparison is reproduced.

Table 1

Composition of the polymer compositions (figures in% by weight)

Table 2

Property comparison

Test methodology

Tensile strength according to DIN 53 455
Elongation according to DIN 53 455
Tear resistance according to DIN 53 315
Shore hardness according to DIN 53 505

Claims (2)

1) Soft, thermoplastically processable polymer alloys with elastic properties, characterized by a content of

• a) 10 to 50% by weight, preferably 10 to 35% by weight, of a thermoplastic, amorphous or partially crystalline, preferably partially crystalline, aliphatic and / or cycloaliphatic polyamide,
• b) 90 to 50% by weight, preferably 90 to 65% by weight, of a partially crosslinked, particulate rubber copolymer
  • b1) at least 60 wt .-%, preferably at least 65 wt .-%, in particular 95 to 60 wt .-%, based on b), of a C₂-C₈ alkyl acrylate with primary or secondary alkyl groups, and
  • b2) 4.45 to 40% by weight, preferably 10 to 35% by weight, in particular 4.45 to 33% by weight, based on b), of at least one monomer from the series of acrylonitrile or C₁-Cmeth-alkyl methacrylates with primary and / or secondary alkyl groups,
  • b3) 0 to 10% by weight, preferably 0 to 6% by weight, in particular 0.5 to 5% by weight, of at least one monomer from the series of a tertiary alkyl (meth) acrylate, (meth) acrylic acid or maleic anhydride , such as
  • b4) 0 to 5% by weight, preferably 0 to 2% by weight, in particular 0.05 to 2% by weight, of a crosslinking monomer with at least two olefinically unsaturated groups,
• wherein the rubber polymer b) has a gel content of 20 to 99% by weight, preferably 50 to 99% by weight, in particular 70 to 99% by weight, and an average particle diameter (d₅₀) of 0.09 to 1.2 µm, preferably 0.09 to 0.8 µm and in particular 0.1 to 0.4 µm.

2. Process for the production of soft, thermoplastically processable polymer alloys with elastic properties by mixing two components by means of known compounding units at elevated temperatures in the melt, characterized in that

• a) 10 to 50 wt .-%, preferably 10 to 35 wt .-%, a thermoplastic, amorphous or partially crystalline aliphatic polyamide, preferably a partially crystalline aromatic polyamide, in particular polyamide-6, polyamide-66, polyamide-11 and / or polyamide -12
  With
• b) 90 to 50% by weight, preferably 90 to 65% by weight, of a partially crosslinked, particulate rubber polymer
  • b1) at least 60% by weight, preferably at least 65% by weight, in particular 95 to 60% by weight, based on b), of a primary C₂-C₈-alkyl acrylate with primary or secondary alkyl groups,
  • b2) 4.45 to 40 wt .-%, preferably 10 to 35 wt .-%, in particular 4.45 to 33 wt .-%, based on b), at least one monomer from the series acrylonitrile or C₁-C₆-alkyl methacrylates with primary and / or secondary alkyl groups,
  • b3) 0 to 10% by weight, preferably 0 to 6% by weight, in particular 0.5 to 5% by weight, of at least one monomer from the series of a tertiary alkyl (meth) acrylate, (meth) acrylic acid or maleic anhydride , such as
  • b4) 0 to 5% by weight, preferably 0 to 2% by weight, in particular 0.05 to 2% by weight, of a crosslinking monomer with at least two olefinically unsaturated groups,
• wherein the rubber polymer b) has a gel content of 20 to 99% by weight, preferably 55 to 99% by weight, in particular 70 to 99% by weight, and an average particle diameter (d₅₀) of 0.09 to 1.2 µm, preferably 0.09 to 0.8 µm and in particular 0.1 to 0.4 µm.
  mixed.